The Role of Non-Covalent Interactions in Electrocatalytic Fuel-Cell Reactions on Platinum

Strmcnik, Dusan S; Kodama, Kensaku; van der Vliet, Dennis; Greeley, Jeffrey P; Stamenkovic, Vojislav R; Markovic, Nenad M

doi:10.1038/nchem.330

Title: The Role of Non-Covalent Interactions in Electrocatalytic Fuel-Cell Reactions on Platinum

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Abstract

The classic models of metal electrode–electrolyte interfaces generally focus on either covalent interactions between adsorbates and solid surfaces or on long-range electrolyte–metal electrostatic interactions. Here we demonstrate that these traditional models are insufficient. To understand electrocatalytic trends in the oxygen reduction reaction (ORR), the hydrogen oxidation reaction (HOR) and the oxidation of methanol on platinum surfaces in alkaline electrolytes, noncovalent interactions must be considered. We find that non-covalent interactions between hydrated alkali metal cations M⁺(H2O)x and adsorbed OH (OHad) species increase in the same order as the hydration energies of the corresponding cations (Li⁺>> Na⁺> K⁺> Cs⁺) and also correspond to an increase in the concentration of OHad–M⁺ (H2O)x clusters at the interface. These trends are inversely proportional to the activities of the ORR, the HOR and the oxidation of methanol on platinum (Cs⁺> K⁺> Na⁺>> Li⁺), which suggests that the clusters block the platinum active sites for electrocatalytic reactions. interface. These trends are inversely proportional to the activities of the ORR, the HOR and the oxidation of methanol on platinum (Cs+> K+> Na+>> Li+), which suggests that the clusters block the platinum active sites for electrocatalytic reactions.

Authors:: Strmcnik, Dusan S; Kodama, Kensaku; van der Vliet, Dennis; Greeley, Jeffrey P; Stamenkovic, Vojislav R; Markovic, Nenad M

Publication Date:: Tue Aug 31 00:00:00 EDT 2010

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Sponsoring Org.:: USDOE

OSTI Identifier:: 990544

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Nature Chemistry, 1(6):466-472

Additional Journal Information:: Journal Volume: 1; Journal Issue: 6

Country of Publication:: United States

Language:: English

Subject:: 08 HYDROGEN; 10 SYNTHETIC FUELS; ALKALI METALS; CATIONS; ELECTROLYTES; ELECTROSTATICS; HYDRATION; HYDROGEN; METHANOL; OXIDATION; OXYGEN; PLATINUM; Environmental Molecular Sciences Laboratory

Citation Formats


                    Strmcnik, Dusan S, Kodama, Kensaku, van der Vliet, Dennis, Greeley, Jeffrey P, Stamenkovic, Vojislav R, and Markovic, Nenad M. The Role of Non-Covalent Interactions in Electrocatalytic Fuel-Cell Reactions on Platinum.  United States: N. p., 2010. 
        Web.  doi:10.1038/nchem.330.

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                    Strmcnik, Dusan S, Kodama, Kensaku, van der Vliet, Dennis, Greeley, Jeffrey P, Stamenkovic, Vojislav R, & Markovic, Nenad M. The Role of Non-Covalent Interactions in Electrocatalytic Fuel-Cell Reactions on Platinum.  United States.  https://doi.org/10.1038/nchem.330

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                    Strmcnik, Dusan S, Kodama, Kensaku, van der Vliet, Dennis, Greeley, Jeffrey P, Stamenkovic, Vojislav R, and Markovic, Nenad M. 2010.  
        "The Role of Non-Covalent Interactions in Electrocatalytic Fuel-Cell Reactions on Platinum".  United States.  https://doi.org/10.1038/nchem.330.

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@article{osti_990544,

  title        = {The Role of Non-Covalent Interactions in Electrocatalytic Fuel-Cell Reactions on Platinum},

  author       = {Strmcnik, Dusan S and Kodama, Kensaku and van der Vliet, Dennis and Greeley, Jeffrey P and Stamenkovic, Vojislav R and Markovic, Nenad M},

  abstractNote = {The classic models of metal electrode–electrolyte interfaces generally focus on either covalent interactions between adsorbates and solid surfaces or on long-range electrolyte–metal electrostatic interactions. Here we demonstrate that these traditional models are insufficient. To understand electrocatalytic trends in the oxygen reduction reaction (ORR), the hydrogen oxidation reaction (HOR) and the oxidation of methanol on platinum surfaces in alkaline electrolytes, noncovalent interactions must be considered. We find that non-covalent interactions between hydrated alkali metal cations M⁺(H2O)x and adsorbed OH (OHad) species increase in the same order as the hydration energies of the corresponding cations (Li⁺>> Na⁺> K⁺> Cs⁺) and also correspond to an increase in the concentration of OHad–M⁺ (H2O)x clusters at the interface. These trends are inversely proportional to the activities of the ORR, the HOR and the oxidation of methanol on platinum (Cs⁺> K⁺> Na⁺>> Li⁺), which suggests that the clusters block the platinum active sites for electrocatalytic reactions. interface. These trends are inversely proportional to the activities of the ORR, the HOR and the oxidation of methanol on platinum (Cs+> K+> Na+>> Li+), which suggests that the clusters block the platinum active sites for electrocatalytic reactions.},

  doi          = {10.1038/nchem.330},

  url          = {https://www.osti.gov/biblio/990544},
  journal      = {Nature Chemistry, 1(6):466-472},
number       = 6,

  volume       = 1,

  place        = {United States},

  year         = {Tue Aug 31 00:00:00 EDT 2010},

  month        = {Tue Aug 31 00:00:00 EDT 2010}

}

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